EP4648613A1 - Gemischte zusammensetzungen zur entfernung biologischer verunreinigungen mit dreiwertigem dotiertem ceroxid und silberzinkzeolith - Google Patents

Gemischte zusammensetzungen zur entfernung biologischer verunreinigungen mit dreiwertigem dotiertem ceroxid und silberzinkzeolith

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Publication number
EP4648613A1
EP4648613A1 EP24706285.4A EP24706285A EP4648613A1 EP 4648613 A1 EP4648613 A1 EP 4648613A1 EP 24706285 A EP24706285 A EP 24706285A EP 4648613 A1 EP4648613 A1 EP 4648613A1
Authority
EP
European Patent Office
Prior art keywords
composition
blended
particulate
oxide
particulate oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24706285.4A
Other languages
English (en)
French (fr)
Inventor
Dimitrios Psaras
Mason Reames Haneline
Steven Paul Williams
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Neo Chemicals and Oxides LLC
Original Assignee
Neo Chemicals and Oxides LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Neo Chemicals and Oxides LLC filed Critical Neo Chemicals and Oxides LLC
Publication of EP4648613A1 publication Critical patent/EP4648613A1/de
Pending legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C02F1/505—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/36—Biological material, e.g. enzymes or ATP
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium

Definitions

  • This disclosure relates to novel blended compositions for biological contaminant removal containing trivalent doped cerium oxide (CeCh) particulate compositions and silver zinc zeolite. These blended compositions can be used as antimicrobial/antibacterial/antiviral agents. As such, this disclosure also relates to the use of these blended compositions for biological contaminant removal.
  • the blended compositions have uses for removing bacteria, viruses, protozoa (e.g., amoebae), fungi (e.g., mold), algae, yeast, and the like. In particular, these compositions can be used in methods for treating fluids, including liquids or air, and solid surfaces through contact.
  • silver has been used widely for its antibacterial activity in medical and consumer products because of its broad range of activity.
  • its application may have negative environmental impacts and it has potential to exert toxic effects on keratinocytes and fibroblasts.
  • silver is known to cause skin irritation; therefore, there has been an effort to minimize its use.
  • This disclosure relates generally to novel blended compositions containing a particulate oxide composition and silver zinc zeolite and the use of these blended compositions for removing biological contaminants.
  • the particulate oxide composition within the blended composition is a trivalent doped cerium oxide, i.e., a mixed oxide of at least cerium and a trivalent dopant.
  • the blended composition comprises less than about 50% to about 1 % by weight of a silver zinc zeolite and greater than about 50% to about 99% by weight of a particulate oxide composition.
  • the particulate oxide composition within the blended composition comprises cerium oxide; trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof; and optionally an additional metal oxide selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof; wherein the cerium oxide is present in an amount greater than the trivalent dopant and wherein the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate oxide composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate composition.
  • trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof
  • the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate composition is about 10% to about 250% greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate oxide composition. In other embodiments, the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate composition is about 15% to about 250% greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate oxide composition.
  • the particulate oxide comprises cerium oxide in an amount of about 99.9 wt % to about 20 wt % based on the total weight of the particulate oxide composition; trivalent dopant in an amount of about 0.1 wt % up to about 50 wt % based on the total weight of the particulate oxide composition; and additional metal oxide in an amount of about 70 wt % to about 0 wt % based on the total weight of the particulate oxide composition. And in specific, there is about 0 wt % additional metal oxide.
  • the blended compositions have biological contaminant removal properties, and as such, have uses for removing bacteria or viruses from fluids, including air and water, and/or from surfaces.
  • the biological contaminants to be removed include bacteria, viruses, protozoa (e.g., amoebae), fungi (e.g., mold or fungus), and the like.
  • the blended compositions allow for reduced amount of silver zinc zeolite while retaining this activity, and the blended compositions exhibit better activity than the silver zinc zeolite or the particulate oxide compositions alone. As such, the blended compositions exhibit unexpected synergistic activity for removing/reducing biological contaminants.
  • supported compositions comprising a support material and the blended compositions.
  • the supported compositions have biological contaminant removal properties, and as such, has uses for removing bacteria or viruses from fluids, including air and water, and/or from surfaces.
  • the supported compositions for removing biological contaminants as disclosed herein comprises a support material comprising an organic polymer, cotton, glass fiber, or mixtures thereof and the blended composition as described herein.
  • the blended composition for biological contaminant removal is deposited on or within the support material.
  • the supported compositions comprise about 0.5 to about 80 weight % blended composition based on the total weight of the supported composition.
  • the supported composition containing the support material and blended composition is in a rigid or elastic form and this supported composition can be made into an article for removing biological contaminants, such as a filter, a fixed bed filter system, a plastic or glass bottle or container, a plastic or glass touch surface, and the like.
  • a plastic article is disclosed.
  • This plastic article comprises: a supported composition for removing biological contaminants comprising (i) an organic polymer selected from the group consisting of polyethylene, polyvinyl chloride, nylon, polypropylene, polyester, polyurethane, polyamide, polyolefin, polycarbonate, copolymers thereof, and mixtures thereof; and (ii) the blended composition as described herein, wherein in the supported composition, the blended composition is deposited on or within the organic polymer.
  • the plastic article comprises about 50 to about 100 weight percent of the supported composition for removing biological contaminants based on the total weight of the plastic article.
  • the plastic article can be a filter, a fixed bed filter system, a plastic bottle or container, a plastic touch surface, a plastic doorknob or handle cover, a plastic elevator button cover, and the like.
  • the blended compositions per se, the supported compositions, and the articles can be used in methods for removing biological contaminants.
  • biological contaminants include bacteria, viruses, protozoa (e.g., amoebae), fungi (e.g., mold or fungus), and the like.
  • the method for removing biological contaminants comprises: (i) providing a blended composition as described herein; (ii) contacting the blended composition with a biological contaminant wherein the biological contaminant is selected from the group consisting of bacteria, viruses, fungi, protozoa (e.g., amoebae), and mixtures thereof; and (iii) removing at least about 90% of the biological contaminant through contact with the blended composition.
  • the blended composition is contained within a filter material or a plastic.
  • the methods treat an aqueous stream, and the biological contaminant is in the aqueous stream.
  • the methods treat a gaseous stream, and the biological contaminant is in the gaseous stream.
  • the contacting is through touch of a solid to the composition and thus treat a solid surface through touch. In certain of these embodiments, the contacting is through touch of a solid to an article comprising the particulate oxide composition.
  • the methods may further comprise a step of setting a target concentration of biological contaminant.
  • a biological contaminant may be identified and a target concentration for that biological contaminant may be set.
  • the methods additionally may comprise a step of monitoring the treated stream for the biological contaminant. The monitoring may be done by sampling or may be continuous.
  • these methods are for removing biological contaminants from fluid and the methods are for treating a fluid.
  • the fluid may be a gaseous or aqueous stream.
  • the methods comprise (i) providing a blended composition as described herein; (ii) contacting a fluid (e.g., a gaseous or aqueous stream) containing biological contaminant with the blended composition, wherein the biological contaminant is selected from the group consisting of bacteria, viruses, fungi (e.g., mold), protozoa (e.g., amoebae), and mixtures thereof; and (iii) removing biological contaminant from the fluid (e.g., gaseous or aqueous stream) through contact with the blended composition.
  • the biological contaminant can be removed in an amount of 90% or more.
  • the blended composition may be used per se and the method may further comprise filtering the fluid/liquid.
  • these methods are for removing biological contaminants from fluid using a supported composition.
  • the fluid may be a gaseous or aqueous stream.
  • the methods comprise (i) providing a supported composition comprising (a) a support material comprising an organic polymer, cotton, glass fiber, or mixtures thereof and (b) the blended composition as described herein; (ii) contacting a fluid containing biological contaminant with the supported composition, wherein the biological contaminant is selected from the group consisting of bacteria, viruses, fungi (e.g., mold), protozoa (e.g., amoebae), and mixtures thereof; and (iii) removing biological contaminant from the fluid through contact with the supported composition.
  • the biological contaminant can be removed in an amount of 90% or more.
  • These methods of treating a fluid or a gaseous or aqueous stream using the blended composition per se or a supported composition may further comprise a step of setting a target concentration of biological contaminant.
  • a biological contaminant of interest is identified and then a target concentration for that biological contaminant is set.
  • the methods additionally may comprise a step of monitoring the biological contaminant in the treated stream. The monitoring may be done by sampling or may be continuous.
  • the blended composition may be used per se by slurrying with the aqueous stream. These methods including slurrying may further comprise a step of filtering.
  • the methods comprise the steps of (i) providing a supported composition comprising (a) a support material comprising an organic polymer, cotton, glass fiber, or mixtures thereof and (b) the blended compositions as described herein; (ii) setting a target concentration of a biological contaminant; (iii) contacting a gaseous or aqueous stream containing biological contaminant with the supported composition and removing biological contaminant through contact with the supported composition to provide a treated stream; and (iv) monitoring the treated stream for the biological contaminant, wherein the biological contaminant is selected from the group consisting of bacteria, viruses, fungi (e.g., mold), protozoa (e.g., amoebae), and mixtures thereof.
  • the biological contaminant is selected from the group consisting of bacteria, viruses, fungi (e.g., mold), protozoa (e.g., amoebae), and mixtures thereof.
  • the target concentration can be set at a certain amount of contaminant (e.g., virus, bacteria, protozoa/amoebae, or fungi) or can be set at the limit of detection.
  • the monitoring may be done by sampling or may be continuous.
  • FIG. 1 is an SEM image of the composition of Example 1 with a scale bar of 200 nm.
  • FIG. 2 is an SEM image of the composition of Example 1 with a scale bar of 2 pm.
  • FIG. 3 is a TEM image of the composition of Example 1 with a scale bar of 10 nm. The light field image is on the left and the dark field image is on the right.
  • FIG. 4 is a TEM image of the composition of Example 1 with a scale bar of 20 nm. The light field image is on the left and the dark field image is on the right.
  • FIG. 5A is the temperature programed desorption of CO2 for the composition of Example 1.
  • FIG. 5B is the temperature programed desorption of CO2 for the composition of Example 2.
  • FIG. 5C is the temperature programed desorption of CO2 for the composition of Example 3.
  • FIG. 6 is the temperature programed desorption of EE for the composition of Example 1, Example 2, and Example 3.
  • FIG. 7 is the zeta-potential vs pH graph for the composition of Example 1, Example 2, and Example 3.
  • FIG. 8 is a graph of the ratio of LaO + /CeO + vs depth for the composition of Example 1 and the composition of Example 2.
  • FIG. 9 is a graph of the ratio of PrO + /CeO + vs depth for the compositions of Example 4 and Example 5.
  • FIG. 10 is an SEM image of the composition of Example 2 with a scale bar of 200 nm.
  • FIG. 11 is an SEM image of the composition of Example 2 with a scale bar of 20 nm.
  • FIG. 12A is a light field TEM image of the composition of Example 2 with a scale bar of 200 nm. The box indicates the zoom area for Fig 12B.
  • FIG. 12C is a light field TEM image of the composition of Example 2 with a scale bar of 5 nm.
  • FIG. 12D is a dark field TEM image of the composition of Example 2 with a scale bar of 5 nm.
  • FIG. 13 is a graph showing the Log removal of MRS A for the series Example 1, Examples 7A-D (blends of Example 1 and 6), and Example 6 (silver zinc zeolite), and this is compared to the series Example 3 (CeCh), Examples 8B-C (blends of Example 3 and 6), and Example 6 (silver zinc zeolite).
  • This disclosure generally relates to blended compositions containing silver zinc zeolite and particulate oxide compositions comprising trivalent doped CeCh.
  • This disclosure also relates to the use of these blended compositions for removing biological contaminants, including bacteria, viruses, and other microbial contaminants, through contact.
  • these blended compositions can remove biological contaminants from air and aqueous liquid streams and can particularly remove bacteria and viruses from air and water whether the microbes are in high or very low concentrations.
  • These blended compositions perform better than silver zinc zeolite alone and allow for use of a reduced amount of silver zinc zeolite while maintaining efficacy for removing biological contaminants.
  • These blended compositions also perform better than the particulate oxide composition alone.
  • reference to “a trivalent dopant” is not to be taken as quantitatively or source limiting
  • reference to “a step” may include multiple steps, reference to “producing” or “products” of a reaction or treatment should not be taken to be all of the products of a reaction/treatment, and reference to “treating” may include reference to one or more of such treatment steps.
  • the step of treating can include multiple or repeated treatment of similar materials/streams to produce identified treatment products.
  • Singular forms of the biological contaminants also include plural referents.
  • “amoeba” and “virus” include reference to “amoebae” and “viruses”, respectively.
  • Numerical values with “about” or “approximately” include typical experimental variances.
  • the terms “about” and “approximately” are used interchangeably and mean within a statistically meaningful range of a value, such as a stated weight percentage, surface area, concentration range, time frame, distance, molecular weight, temperature, pH, and the like. Such a range can be within an order of magnitude, typically within 10%, and even more typically within 5% of the indicated value or range. Sometimes, such a range can be within the experimental error typical of standard methods used for the measurement and/or determination of a given value or range. The allowable variation encompassed by the term “about” will depend upon the particular system under study, and can be readily appreciated by one of ordinary skill in the art. Whenever a range is recited within this application, at least every whole number integer within the range is also contemplated as an embodiment of the invention.
  • the disclosed blended compositions have activity for removing biological contaminants.
  • These blended compositions contain trivalent doped CeCh particulate compositions and silver zinc zeolite.
  • the trivalent doped CeCh particulate compositions are also described as particulate oxide compositions and these terms are used interchangeably herein.
  • This particulate oxide compositions are composed of mixed oxides of Ce and a trivalent dopant.
  • the blended compositions as disclosed herein are for biological contaminant removal and contain less than about 50% to about 1 % by weight of a silver zinc zeolite; and (b) greater than about 50% to about 99% by weight of a particulate oxide composition.
  • This particulate oxide composition comprises cerium oxide; trivalent dopant (as an oxide) selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof; and optionally an additional metal oxide selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof.
  • the cerium oxide is present in an amount greater than the trivalent dopant and the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate oxide composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate composition.
  • the particulate oxide composition comprises cerium oxide in an amount of about 99.9 wt % to about 20 wt % based on the total weight of the particulate oxide composition; trivalent dopant in an amount of about 0.1 wt % up to about 50 wt % based on the total weight of the particulate oxide composition; and additional metal oxide in an amount of about 70 wt % to about 0 wt % based on the total weight of the particulate oxide composition.
  • the blended compositions as disclosed herein contain less than about 50% to about 1% by weight of silver zine zeolite and greater than about 50% to about 99% by weight of the particulate oxide composition.
  • the blended compositions comprise about 35% to about 5 % by weight of silver zinc zeolite and about 65% to about 95% by weight of the particulate oxide composition. In particular embodiments, the blended compositions comprise about 25% to about 10 % by weight of silver zinc zeolite and about 75% to about 90% by weight of the particulate oxide composition.
  • the silver zinc zeolite (Ze-Ag-Zn: CAS No. 130328-20-0) is a silver and zinc ion surface-modified Linde Type A (LTA) zeolite framework with applications, such as in antimicrobial coatings.
  • LTA zeolite is a crystalline aluminosilicate of well-defined three-dimensional framework that has been surface-modified with both silver and zinc ions.
  • the Ag + content can be approximately 0.4 wt % to approximately 6 wt % and the Zn 2+ content can be approximately 1 wt % to approximately 16 wt %.
  • the particulate oxide composition is composed primarily of mixed oxides of Ce and a trivalent dopant. These particulate oxide compositions are also described herein as trivalent doped CeCh compositions or trivalent doped CeCh particulate compositions.
  • the trivalent doped CeCh particulate compositions are mixed oxides of Ce and of a trivalent dopant.
  • the trivalent dopant is selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof.
  • the particulate oxide compositions also contain an amount of additional metal oxide.
  • This additional metal oxide is selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof.
  • the blended compositions as disclosed herein perform better than silver zinc zeolite alone and allow for use of a reduced amount of silver zinc zeolite while maintaining efficacy for removing biological contaminants.
  • the blended compositions as disclosed herein also perform better than the particulate oxide composition alone.
  • the trivalent doped CeCh compositions or particulate oxide compositions comprise cerium oxide and one or more trivalent dopants (as oxides) and optionally one or more additional metal oxides.
  • the particulate oxide composition comprises cerium oxide, trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof (as oxides), optionally one or more additional metal oxides, other than the cerium oxide and trivalent dopant, and/or trace amounts of impurities.
  • the additional metal oxides within the particulate oxide composition are selected from the group consisting of aluminum, titanium, zirconium, hafnium, and mixtures thereof. In certain embodiments, the particulate oxide composition contains about zero additional metal oxides. In other embodiments, the particulate oxide composition contains additional metal oxides.
  • the particulate oxide compositions exhibit activity for removing/reducing biological contaminants and are used in the blended compositions also containing silver zinc zeolite.
  • the blended compositions allow for reduced amount of silver zinc zeolite while retaining activity, and the blended compositions tend to exhibit better activity than the silver zinc zeolite or the particulate oxide compositions alone.
  • the blended compositions exhibit unexpected synergistic activity for removing/reducing biological contaminants.
  • the cerium of the cerium oxide in the particulate oxide composition is Ce(IV).
  • the trivalent rare earth dopants can be selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), cerium (Ce), and mixtures thereof.
  • the trivalent dopant is yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof, and in particular embodiments, the trivalent dopant is Nd, La, or a mixture thereof. In other embodiments, the trivalent dopant is La. In additional embodiments, the trivalent dopant is Pr. As described, the trivalent dopant is present within the particulate composition as an oxide so that the particulate oxide composition comprises a mixed oxide of at least cerium and trivalent dopant.
  • the trivalent dopant is present in a minority amount in comparison to the cerium oxide, and as such, the particulate oxide compositions contain more cerium oxide than trivalent dopant (also present as an oxide).
  • the particulate oxide composition optionally also may contain additional metal oxides, other than the cerium oxide and trivalent dopant. These additional metal oxides may be selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof.
  • the particulate oxide composition is a mixed oxide composition (i.e., a mixture of oxides of at least cerium and trivalent dopant).
  • the composition also is identified herein as a trivalent doped cerium oxide, and when identified as such, it is a mixed cerium trivalent dopant oxide, but this description does not exclude the additional metal oxides, unless it is identified that the composition contains about zero additional metal oxides, other than the cerium and trivalent dopant.
  • the trivalent dopant is La and the particulate oxide composition does contain about zero additional metal oxides.
  • the particulate oxide composition is a mixed cerium lanthanum oxide (or a La doped cerium oxide).
  • the particulate oxide composition comprises the trivalent dopant (as an oxide) in an amount of about 0.1 wt % up to about 50 wt % based on the total weight of the particulate oxide composition. As stated above, the trivalent dopant is present in a minority amount in comparison to the cerium oxide. In certain embodiments, the particulate oxide composition contains the trivalent dopant in an amount of about 0.5 wt % to about 40 wt % or in an amount of about 1 wt % to about 40 wt % based on the total weight of the particulate oxide composition.
  • the particulate oxide composition contains the trivalent dopant in an amount of about 2 wt % to about 35 wt % or in an amount of about 2 wt % to about 30 wt % based on the total weight of the particulate oxide composition. In additional embodiments, the particulate oxide composition contains the trivalent dopant in an amount of about 2 wt % to about 25 wt % or in an amount of about 5 wt % to about 20 wt % based on the total weight of the particulate oxide composition. In specific of these embodiments, the particulate oxide composition contains the trivalent dopant in an amount of about 15 wt % based on the total weight of the particulate oxide composition.
  • the trivalent dopant is present within the particulate composition as an oxide and these wt% are based on trivalent dopant as an oxide.
  • the trivalent dopant is lanthanum and the particulate oxide composition is cerium oxide doped with lanthanum (i.e., a mixed oxide of cerium and lanthanum).
  • the amount of cerium oxide will correspond to and vary with the amount of trivalent dopant so that the total amount of the trivalent dopant (as an oxide) and cerium oxide is about 100% of the particulate composition.
  • the trivalent dopant is lanthanum
  • the particulate oxide composition is cerium oxide doped with lanthanum.
  • the cerium oxide is present in an amount greater than trivalent dopant.
  • the particulate oxide composition as disclosed herein generally comprises the cerium oxide in an amount of about 99.9 wt % to about 20 wt % based on the total weight of the particulate oxide composition.
  • the particulate oxide composition contains the cerium oxide in an amount of about 99.9 wt % to about 50 wt %.
  • the particulate oxide composition contains the cerium oxide in an amount of about 99.5 wt % to about 25 wt % or in an amount of about 99 wt % to about 30 wt % based on the total weight of the particulate oxide composition.
  • the particulate oxide composition contains the cerium oxide in an amount of about 98 wt % to about 65 wt % or in an amount of about 98 wt % to about 70 wt % based on the total weight of the particulate oxide composition. In additional embodiments, the particulate oxide composition contains the cerium oxide in an amount of about 98 wt % to about 75 wt % or in an amount of about 95 wt % to about 80 wt % based on the total weight of the particulate oxide composition. In specific of these embodiments, the particulate oxide composition contains the cerium oxide in an amount of about 85 wt % based on the total weight of the particulate oxide composition. The amount of cerium oxide will vary with and correspond to the amount of trivalent dopant, and any amount of optional additional metal oxide, so that the total amount is about 100% of the particulate composition.
  • the particulate oxide composition comprises about zero wt % additional metal oxides, and in these embodiments, the particulate oxide composition comprises the cerium oxide in an amount to provide about 100% of the particulate composition based on the weight % of trivalent dopant.
  • the composition contains cerium oxide in an amount of about 99.9 wt % to about 50 wt %.
  • the composition contains cerium oxide in an amount of about 99 wt% to about 60 wt %. In an embodiment containing the trivalent dopant in an amount of about 2 wt % to about 30 wt % based on the total weight of the particulate oxide composition, the composition contains cerium oxide in an amount of about 98 wt % to about 70 wt %, and the like.
  • the particulate oxide composition optionally may contain additional metal oxides other than the cerium oxide and trivalent dopant.
  • additional metal oxides may be selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof.
  • the particulate oxide composition as disclosed herein generally comprises the additional metal oxide in an amount of about 70 wt % to about 0 wt % based on the total weight of the particulate oxide composition.
  • the particulate oxide comprises cerium oxide in an amount of about 99.9 wt % to about 20 wt % based on the total weight of the particulate oxide composition; trivalent dopant in an amount of about 0.1 wt % up to about 50 wt % based on the total weight of the particulate oxide composition; and additional metal oxide in an amount of about 70 wt % to about 0 wt % based on the total weight of the particulate oxide composition.
  • the cerium oxide is present in an amount greater than trivalent dopant.
  • the particulate oxide composition generally comprises these additional metal oxides in an amount of about 70 wt % to about 0.1 wt % based on the total weight of the particulate oxide composition. In certain embodiments, the particulate oxide composition contains these additional metal oxides in an amount of about 50 wt % to about 0.1 wt % or in an amount of about 30 wt % to about 0.1 wt % based on the total weight of the particulate oxide composition. In certain embodiments, the particulate oxide composition contains these additional metal oxides in an amount of about 10 wt % to about 0.1 wt % based on the total weight of the particulate oxide composition.
  • the particulate oxide composition contains about zero wt % additional metal oxides.
  • the amount of additional metal oxide will vary with and correspond to the amount of trivalent dopant and cerium oxide so that the total amount is about 100% of the particulate composition.
  • the particulate oxide composition comprises trivalent dopant in an amount of about 2 wt % to about 25 wt % based on the total weight of the particulate oxide; cerium oxide in an amount of about 20 wt % to about 30 wt %; and additional metal oxide in an amount of about 45 wt % to about 78 wt %.
  • the cerium oxide is present in an amount greater than trivalent dopant and the amounts of the components will vary and correspond so that the total amount is about 100% of the particulate composition.
  • the particulate oxide composition comprises trivalent dopant in an amount of about 2 wt % to about 25 wt % based on the total weight of the particulate oxide; cerium oxide in an amount of about 45 wt % to about 78 wt %; and additional metal oxide in an amount of about 20 wt % to about 30 wt %.
  • the cerium oxide is present in an amount greater than trivalent dopant and the amounts of the components will vary and correspond so that the total amount is about 100% of the particulate composition.
  • the particulate oxide composition optionally may further contain impurities in a minor amount. These impurities are typically present in an amount of about 1% by weight or less (to about zero or to an amount that is undetectable) based on the total weight of the particulate oxide composition. These impurities include residual solvents, salts, other metals, and the like. These other metals include those commonly found in water, such as magnesium, iron, calcium, silicon, sodium, and the like. These impurity amounts (of about 1% by weight to about zero or to an amount that is undetectable) may be present in any of the above and below described embodiments of the particulate oxide compositions. When present and detectable, any impurities are generally present in an amount of about 100 ppm or less.
  • the particulate oxide compositions as disclosed herein have a unique depth profile for the distribution of the cerium oxide and the trivalent dopant. This unique depth profile means that there is a higher ratio of trivalent dopant to Ce closer to the surface of the particulate oxide composition in comparison to deeper within the particulate oxide composition.
  • the unique depth profile for the particulate oxide compositions provides unique structural (ie., physical) and electrochemical properties and provides improved activity for removing biological contaminants when used in the blended compositions as disclosed herein.
  • the depth profile one of skill in the art recognizes that these particulate oxide compositions have a surface, and this surface is referred to as at about 0 nm.
  • the unique depth profile of the particulate oxide composition is characterized such that the average trivalent dopant to Ce ratio at about 0 nm (z.e., the surface) to about 3.5 nm from the surface of the particulate oxide composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate oxide composition. Measurements of the Ce and trivalent dopant are taken at certain intervals from 0 nm (z.e., the surface) to about 3.5 nm and then averaged. Measurement of the Ce and trivalent dopant is also taken at about 15 nm from the surface of the particulate composition.
  • Figure 8 is a graph of the ratio of LaO + /CeO + vs depth and demonstrates this unique depth profile for one example of particulate oxide composition to be used within the blended compositions.
  • the depth profile for the distribution of cerium oxide and trivalent dopant is measured by Time of Flight (ToF) Secondary Ion Mass Spectrometry (SIMS) Depth profilometry as described in Noel, C. et al. ToF-SIMS Depth Profiling of Organic Delta Layers with Low-Energy Cesium Ions: Depth Resolution Assessment, Journal of The American Society for Mass Spectrometry, Vol. 30 (2019) pp 1537-1544, the contents of which are incorporated by reference in their entirety.
  • TOF Time of Flight
  • SIMS Secondary Ion Mass Spectrometry
  • a square section of a particle of the sample material is chosen and analyzed by ToF-SIMS which yields the analysis at a depth of 0 nm (z.e., at the surface).
  • ToF-SIMS works by bombarding the target material with an ion beam, which causes the material to sputter.
  • Sputtering is a phenomenon where microscopic particles are ejected from the surface of a solid material. The ejected particles are then analyzed by mass in the mass spectrometer.
  • the ion source for the ToF-SIMS analysis in this disclosure was a cesium ion source run at 2 keV with a target current of 130 nA; the sputtering size was 500 pm 2 ; the analysis area was 200 pm 2 , 2 frames analysis followed by 6 frames sputter, and 60 seconds sputter time.
  • the selected square section is then etched with an ion beam to remove the surface atoms.
  • a primary ion beam was a bismuth liquid metal ion gun run at 30 keV with pulsed target current of approximately 0.6 pA; the sputtering size was 250 pm 2 ; the analysis area was 100 pm 2 , 2 frames analysis followed by 50 frames sputter, and 20,000 seconds sputter time.
  • the time of the etching is correlated to the depth of the etching, and thus the depth can be controlled.
  • the sputter depth was calibrated to 1 nm/s. The exposed surface is then reanalyzed by ToF-SIMS to give the analysis at the new depth.
  • the particulate composition can be analyzed in any increments of nm, for example, in increments of about 0.2 nm, increments of about 0.5 nm, increments of about 1 nm, and the like. This process is repeated until the desired depth is obtained. The observed mass spectrometry data is then correlated to the depth at which it was collected. For the present disclosure, it is important to determine the ratio of trivalent dopant to Ce, and thus, this is the reported data.
  • the particulate oxide composition of the blended composition comprises cerium oxide, trivalent dopant (as an oxide) selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof, and optionally an additional metal oxide selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof, wherein the cerium oxide is present in an amount greater than the trivalent dopant and wherein the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate oxide composition.
  • trivalent dopant as an oxide
  • Y yttrium
  • La lanthanum
  • Nd neodymium
  • Pr praseodymium
  • Hf hafn
  • the composition comprises about 0.1 wt % up to about 50 wt % trivalent dopant. In a certain embodiment, the composition further comprises about 99.9 wt % to about 50 wt % cerium oxide based on the total weight of the particulate oxide composition.
  • a particulate oxide composition comprising cerium oxide and trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof, and optionally an additional metal oxide selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof, wherein the cerium oxide is present in an amount greater than the trivalent dopant, wherein the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate oxide composition, and wherein the composition comprises about 2 wt % to about 30 wt % trivalent dopant.
  • the composition comprises cerium oxide in an amount of about 98
  • the particulate oxide compositions containing trivalent doped CeCh having the described depth profile can have any of the abovedescribed amounts of trivalent dopant, cerium oxide, and optional additional metal oxide.
  • the particulate oxide composition contains cerium oxide and trivalent dopant with only minor amounts to no (z.e., about zero) additional metal oxides and only 1% to no (z.e., zero or undetectable) amounts of impurities. When present and detectable, any impurities are generally present in an amount of about 100 ppm or less.
  • the particulate oxide compositions have an average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate oxide composition that is about 10% to about 250% greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate oxide composition.
  • the particulate oxide compositions have an average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate oxide composition that is about 15% to about 250% greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate oxide composition.
  • 0 nm from the surface of the particulate oxide composition is the surface of the particulate oxide composition.
  • particulate oxide compositions containing trivalent doped CeCh having the above-described depth profile also can have any of the above-described amounts of trivalent dopant, cerium oxide, and optional additional metal oxide, and the below described additional properties.
  • the particulate oxide compositions containing trivalent doped CeCh having the unique depth profile also can exhibit unique physical characteristics, including for example, exhibiting both physisorption and chemisorption of CO2 (see Figures 5A, 5B, and 5C).
  • Physisorption also is known as physical adsorption and is a weak association, such as through van der Waals.
  • Chemisorption also is known as chemical adsorption. In chemisorption, adsorption takes place, and the adsorbed substance is bound by chemical bonds. This is a much stronger adsorption than physisorption. Exhibiting physisorption and chemisorption is a unique characteristic of the particulate compositions containing trivalent doped CeCh having the above-described depth profile.
  • the adsorbant is CO2 (an acid)
  • exhibiting chemisorption indicates the material is more basic and may provide improved activity for removing biological contaminants.
  • This property of exhibiting physisorption and chemisorption may be combined with any of the above-described depth profiles and any of the abovedescribed amounts of trivalent dopant, cerium oxide, and optional additional metal oxide, as well as the below described additional properties.
  • the particulate oxide compositions with the unique depth profile also can be more readily reduced than compositions made by prior art methods, and thus, these compositions are more oxidizing.
  • Figure 6 is a graph of the temperature program hydrogen reduction of material from Examples 1, 2, and 3.
  • Example 1 has a large sharp peak at a lower temperature. This peak indicates that this novel particulate oxide composition is more easily reduced as compared to the compositions of Example 2 or 3.
  • the graph for Example 2 has essentially the same shape as Example 1 but it is shifted to higher temperatures, which indicates more energy is needed for the material to react with hydrogen and would thus it would be less oxidizing than Example 1.
  • the graph for Example 3 which is undoped cerium oxide, shows two peaks for hydrogen reduction that are broad and not very tall. This would indicate there are two types of reductions that could take place with this material and the higher temperature one is much more difficult to achieve.
  • the unique depth profile for the particulate oxide compositions such that there is a higher ratio of trivalent dopant to Ce on and closer to the surface of the particulate matter, could lead to this change in hydrogen reduction temperature and more oxidative properties. And these more oxidative properties of the particulate oxide compositions having the unique depth profile can provide improved activity for removing biological contaminants.
  • the particulate oxide compositions containing trivalent doped CeCh and having the unique depth profile as disclosed herein further can exhibit more basicity as indicated by its isoelectric point and zeta potential (see Figure 7).
  • the particulate oxide composition as described herein has an isoelectric point at a pH of about 8 to about 9.
  • the particulate oxide composition as described herein has a zeta potential of about 20 to about 40 mV at a pH of about 7.
  • Having a higher isoelectric point indicates the material is more basic and may provide improved activity for removing biological contaminants. This property also can be combined with any of the above-described depth profiles, physical properties, and any of the above-described amounts of trivalent dopant, cerium oxide, and optional additional metal oxide, as well as the below described additional properties.
  • the particulate oxide compositions containing trivalent doped CeCh also can have a surface area that assists in providing the biological contaminant removal properties.
  • the surface area is the apparent surface area of the compositions as determined by using a Micromeritics ASAP 2000 system and nitrogen at about 77 Kelvin. The procedure outlined in ASTM International test method D 3663 - 03 (Reapproved 2008) was used but with one significant exception. It is well known that a "BET Surface Area" determination is not possible for materials that contain microporosity. Recognizing that the surface area is an approximation, the values reported are labeled "apparent surface area” values rather than "BET surface area” values. In compliance with commonly accepted procedures, the determination of apparent surface area, the application of the BET equation was limited to the pressure range where the term na(l - P/Po) of the equation continuously increases with P/Po. The out gassing of the sample was done under nitrogen at about 300 degrees Celsius for about 2 hours.
  • the particulate oxide compositions containing trivalent doped CeCh can have a surface area of about 70 m 2 /g to about 300 m 2 /g. While not wanting to be bound by any theory, it is believed that the surface area can affect and improve the removal of the biological contaminant from a gaseous or an aqueous stream or by contact with a solid surface. [0090] It can be appreciated that the particulate oxide compositions having this surface area can have the below-described average pore volume in combination with any one or more of the depth profile and the other above-described properties, as well as any of the above-described amounts of trivalent dopant, cerium oxide, and optional additional metal oxide.
  • the particulate oxide compositions typically have an average (mean, median, and mode) pore volume (as determined by N2 adsorption) of about 0.01 cm 3 /g to about 1.5 cm 3 /g. While not wanting to be bound by any theory it is believed that the average pore volume can affect and improve the removal of the biological contaminant from an aqueous or gaseous stream.
  • the particulate oxide compositions can have the above-described average pore volumes in combination with any one or more of the above surface areas, depth profile, and the other above-described properties, as well as any of the above-described amounts of trivalent dopant, cerium oxide, and optional additional metal oxide.
  • blended compositions as disclosed herein perform better than silver zinc zeolite alone and allow for use of a reduced amount of silver zinc zeolite while maintaining efficacy for removing biological contaminants.
  • the blended compositions allow for reduced amount of the silver zinc zeolite while retaining activity, and the blended compositions tend to exhibit better activity than the silver zinc zeolite or the particulate oxide compositions alone. As such, the blended compositions exhibit unexpected synergistic activity for removing/reducing biological contaminants.
  • the novel blended compositions contain silver zinc zeolite and particulate oxide compositions, both as described above.
  • the blended compositions comprise the silver zinc zeolite in an amount of about 1 wt % to less than about 50 wt % based on the total weight of the blended composition and the particulate oxide composition in an amount of greater than about 50 wt % to about 99 wt % based on the total weight of the blended composition.
  • the blended compositions comprise about 10 wt % to about 25 wt % silver zinc zeolite and about 75 wt % to about 90 wt % particulate oxide composition.
  • the silver zinc zeolite is present in a minority amount in comparison to the particulate oxide composition.
  • the particulate oxide compositions in the blended compositions include all of the embodiments for the particulate oxide composition as described supra. In particular the particulate oxide compositions in the blended compositions are those with the unique depth profile as described herein.
  • the blended compositions can be slurried with a biological contaminantcontaining aqueous stream and effectively remove the biological contaminants.
  • slurrying the blended compositions with a biological contaminantcontaining aqueous stream removes at least about 90% of the biological contaminant.
  • the slurrying removes at least 95%, or more preferably 99% or 99%+ of the biological contaminant.
  • blended compositions as described herein also can be incorporated into supported compositions and/or articles for removing biological contaminants as described infra.
  • supported compositions comprising a support material and the blended compositions containing silver zinc zeolite and trivalent doped CeCh particulate compositions. These supported compositions are for removing biological contaminants.
  • the supported compositions comprise a support material and the blended compositions containing silver zinc zeolite and particulate oxide composition comprising cerium oxide doped with a trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof, and optionally an additional metal oxide selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof, wherein the cerium oxide is present in an amount greater than the trivalent dopant.
  • a trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr),
  • the particulate oxide composition comprises cerium oxide, one or more trivalent dopants (as oxides), and optionally the additional metal oxides, other than the cerium oxide and trivalent dopant, and/or trace amounts of impurities.
  • the particulate oxide composition contains about zero additional metal oxides.
  • the particulate oxide composition has the unique depth profile wherein the cerium oxide is present in amount greater than the trivalent dopant and wherein the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate oxide composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate composition.
  • the particulate oxide compositions in the blended compositions within the supported compositions include all of the embodiments for the particulate oxide composition as described supra.
  • the supported compositions for removing biological contaminants also comprise a support material.
  • This support material comprises an organic polymer, cotton, glass fiber, or mixtures thereof.
  • the organic polymer can be a homopolymer of organic monomers or a copolymer.
  • the organic polymer also can be a thermoset polymer, such as a thermoplastic elastomer.
  • the organic polymer is selected from the group consisting of polyethylene, polycarbonate, polyvinyl chloride, nylon, polypropylene, polyester, polyurethane, polyamide, polyolefin, copolymers thereof, and mixtures thereof.
  • the organic polymer is silicone.
  • the blended composition is deposited on or within the support material.
  • the particulate oxide composition of the blended composition, comprises cerium oxide in an amount of about 99.9 wt % to about 20 wt % based on the total weight of the particulate oxide composition; trivalent dopant (as an oxide) in an amount of about 0.1 wt % up to about 50 wt % based on the total weight of the particulate oxide composition; and additional metal oxide in an amount of about 70 wt % to about 0 wt % based on the total weight of the particulate oxide composition.
  • the particulate oxide composition of the blended composition, comprises about 0.1 wt % up to about 50 wt % trivalent dopant and about 99.9 wt % to about 50 wt % cerium oxide based on the total weight of the particulate oxide composition.
  • the particulate oxide composition of the blended composition, comprises cerium oxide in an amount of about 20 wt % to about 30 wt % based on the total weight of the particulate oxide composition; trivalent dopant in an amount of about 2 wt % to about 25 wt % based on the total weight of the particulate oxide composition; and additional metal oxide in an amount of about 45 wt % to about 78 wt % based on the total weight of the particulate oxide composition.
  • the particulate oxide composition of the blended composition, comprises cerium oxide in an amount of about 45 wt % to about 78 wt % based on the total weight of the particulate oxide composition; trivalent dopant in an amount of about 2 wt % to about 25 wt % based on the total weight of the particulate oxide composition; and additional metal oxide in an amount of about 20 wt % to about 30 wt % based on the total weight of the particulate oxide composition.
  • the blended compositions can have any of the above-described amounts of particulate oxide composition and silver zinc zeolite.
  • These supported compositions comprise a support material comprising an organic polymer, cotton, glass fiber, or mixtures thereof and the blended composition containing silver zinc zeolite and particulate oxide composition having the unique depth profile.
  • this particulate oxide composition is a mixed oxide composition (i.e., a mixture of oxides of the cerium, trivalent dopant, and optionally additional metal oxides).
  • the blended composition containing silver zinc zeolite and particulate oxide composition i.e., the trivalent doped cerium oxide having the unique depth profile
  • the particulate oxide composition of this supported composition includes all of the embodiments as described supra, including all of the properties and any of the abovedescribed amounts of trivalent dopant, cerium oxide, and optional additional metal oxide.
  • the supported compositions contain approximately 0.5 to approximately 80 weight % blended composition based on the total weight of the supported composition. In certain embodiments, the supported compositions contain approximately 0.5 to approximately 50 weight % blended composition based on the total weight of the supported composition.
  • the supported compositions contain approximately 0.5 to approximately 25 weight % blended composition based on the total weight of the supported composition. In yet other embodiments, the supported compositions contain approximately 0.5 to approximately 10 weight % blended composition based on the total weight of the supported composition. In additional embodiments, the supported compositions contain approximately 0.5 to approximately 5 weight % blended composition based on the total weight of the supported composition. In these supported compositions, it can be appreciated that the blended compositions can have any of the above-described amounts of particulate oxide composition and silver zinc zeolite.
  • the supported composition containing the support material and the blended composition can be in a rigid or elastic form.
  • the supported composition can form an article for removing biological contaminants, such as a filter or a plastic (such as a plastic container).
  • the article can be in a rigid or elastic form.
  • the article contains about 50 to about 100 weight % of the supported composition containing the support material and the blended composition based on the total weight of the article. In certain embodiments, the article contains about 75 to about 95 weight % of the supported composition containing the support material and the blended composition based on the total weight of the article.
  • the blended composition and support are formed into an elastic or rigid article
  • the article also may include binder, sand, gravel, glass wool, a metal or plastic container, and the like.
  • the support material can be an organic polymer.
  • the trivalent dopant of the particulate oxide composition is Pr, La, or a mixture thereof.
  • the article can be a plastic article.
  • the organic polymer can be selected from the group consisting of polyethylene, polyvinyl chloride (PVC), nylon, polypropylene, polyester, polyurethane, polyamide, polyolefin, polycarbonate, copolymers thereof, and mixtures thereof.
  • the organic polymer is polyethylene, polycarbonate, or mixtures thereof.
  • the article can be in the form of a filter, bottle, container, or a plastic covering for a high touch service.
  • the filter can be a fixed bed.
  • the bottle or container may be for liquids.
  • High touch surfaces include escalator or stair handrail covering, an elevator button covering, a door, a door handle or knob or covering therefore, coverings on public transportation, touch pads for electronic transactions, and the like.
  • the support material can be cotton.
  • the trivalent dopant of the particulate oxide composition is Pr, La, or a mixture thereof.
  • the article can be a filter or a fabric.
  • the support material can be glass fiber.
  • the trivalent dopant of the particulate oxide composition is Pr, La, or a mixture thereof.
  • the article can be a filter, bottle, container, or high touch surface.
  • the filter can be a fixed bed. High touch surfaces include an elevator button covering, a door, coverings on public transportation, touch pads for electronic transactions, and the like.
  • the support material can be cotton and an organic polymer.
  • the organic polymer can be selected from the group consisting of nylon, polyester, polyamide, and mixtures thereof.
  • the trivalent dopant of the particulate oxide composition is Pr, La, or a mixture thereof. When this mixture as the support material forms an article, the article can be a filter or a fabric.
  • the support material can be glass fiber and an organic polymer.
  • the organic polymer can be selected from the group consisting of polyethylene, polyvinyl chloride (PVC), nylon, polypropylene, polyester, polyurethane, polyamide, polyolefin, polycarbonate, copolymers thereof, and mixtures thereof.
  • the organic polymer can be selected from the group consisting of polyethylene, polycarbonate, and mixtures thereof.
  • the trivalent dopant of the particulate oxide composition is Pr, La, or a mixture thereof.
  • the article can be a filter, bottle, container, or high touch surface.
  • the filter can be a fixed bed. High touch surfaces include escalator or stair handrail covering, an elevator button covering, a door, a door handle or knob covering, coverings on public transportation, touch pads for electronic transactions, and the like.
  • the support material can be polyethylene or polycarbonate.
  • the trivalent dopant of the particulate oxide composition is Pr, La, or a mixture thereof.
  • the article when the supported composition forms an article, the article can be a plastic article and can be in the form of a filter, bottle, container, or plastic covering for a high touch surface.
  • the filter can be a fixed bed.
  • the support material can be silicone.
  • the trivalent dopant of the particulate oxide composition is Pr, La, or a mixture thereof.
  • the article is a plastic article.
  • the plastic article can be in the form of a filter, bottle, container, or plastic covering for a high touch surface.
  • the plastic article comprises a supported composition for removing biological contaminants comprising (i) an organic polymer selected from the group consisting of polyethylene, polyvinyl chloride, nylon, polypropylene, polyester, polyurethane, polyamide, polyolefin, polycarbonate, copolymers thereof, and mixtures thereof.
  • the plastic article further comprises the blended composition comprising (i) silver zinc zeolite and (ii) particulate oxide composition comprising cerium oxide; trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof; and optionally an additional metal oxide selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof, wherein the cerium oxide is present in an amount greater than the trivalent dopant and wherein the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate oxide composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate composition.
  • Y yttrium
  • La lanthanum
  • Nd neodymium
  • Pr praseodymium
  • the trivalent dopant of the particulate oxide composition is Pr, La, or a mixture thereof.
  • the organic polymer can be selected from the group consisting of polyethylene, polycarbonate, and mixtures thereof.
  • the blended composition is deposited on or within the organic polymer.
  • the plastic article comprises about 50 to about 100 weight percent of the supported composition for removing biological contaminants based on the total weight of the plastic article.
  • the plastic article comprises a blended composition containing (i) silver zinc zeolite and (ii) a particulate oxide composition comprising about 0.1 wt % up to about 50 wt % trivalent dopant and about 99.9 wt % to about 50 wt % cerium oxide based on the total weight of the particulate oxide composition.
  • This specific particulate oxide composition includes all of the embodiments for the particulate oxide composition as described supra.
  • the blended compositions containing silver zinc zeolite and trivalent doped cerium oxide particulate compositions, the supported compositions, and the articles as disclosed herein are capable of removing approximately 90% or more of the biological contaminants. In certain embodiments, the blended compositions, supported compositions, and articles as disclosed herein are capable of removing approximately 99% or more of the biological contaminants.
  • the biological contaminants to be removed by the articles, supported compositions, blended compositions, and methods disclosed herein include viruses, bacteria, fungi, (e.g., mold or fungus), protozoa (e.g., amoebae), algae, yeast, and the like, and mixtures thereof.
  • the biological contaminants to be removed by the articles, compositions, and methods disclosed herein are selected from the group consisting of bacteria, viruses, fungi (e.g., mold), protozoa (e.g., amoebae), and mixtures thereof.
  • the biological contaminants to be removed by the articles, compositions, and methods disclosed herein are bacteria, viruses, amoebae, and mixtures thereof.
  • the biological contaminants are bacteria, viruses, and mixtures thereof.
  • the biological contaminants to be removed include those of concern in aqueous streams, such as wastewater, and those of concern which are airborne.
  • the bacteria include gram positive and gram negative bacteria.
  • the bacteria include those commonly found in water, including fecal coliform bacteria.
  • the bacteria include, for example, Streptococcus, Staphylococcus, Escherichia coli, Methicillin- resistant Staphylococcus aureus (MRSA), Legionella Pneumophila, Campylobacter Jejuni, Salmonella, Mycobacterium tuberculosis, Corynebacterium diphtheriae, Listeria monocytogenes, Bordetella pertussis, and the like.
  • the viruses include, for example, rhinovirus, coronaviruses, vaccinia, poliovirus, varicella zoster virus, paramyxovirus, influenza virus, morbillivirus, hepatitis A virus (HAV), adenovirus (HAdV), rotavirus (RoV), sapovirus, respiratory syncytial virus (RSV), paramyxovirus, varicella-zoster virus (VZV), variola virus (including smallpox and monkey pox), and other enteric viruses, such as noroviruses (NoV), coxsackievirus, echovirus, reovirus and astrovirus, and the like.
  • enteric viruses such as noroviruses (NoV), coxsackievirus, echovirus, reovirus and astrovirus, and the like.
  • microbial contaminants include protozoa (such as Cryptosporidium) and specifically amoebae (such as Naegleria fowleri). Further microbial contaminants, which are fungi, include Trichophyton mentagrophytes and Aspergillus.
  • Trivalent Doped Cerium Oxide Particulate Oxide Composition There are known methods for making trivalent doped cerium oxide compositions (see for example U.S. Patent Application No. 17/870,068 entitled “Use of Trivalent Doped Cerium Oxide Compositions for Biological Contaminant Removal” filed July 21, 2021, the contents of which are hereby incorporated by reference in their entirety).
  • the methods for making trivalent doped cerium oxide compositions with the unique depth profile as described herein are described in U.S. Patent Application No. 17/895,942, entitled “Trivalent Doped Cerium Oxide Compositions for Biological Contaminant Removal” filed August 25, 2022, the contents of which are hereby incorporated by reference in their entirety.
  • the blended compositions as disclosed herein contain the particulate oxide composition and silver zinc zeolite.
  • the method of making the blended compositions includes physically mixing the silver zinc zeolite with the particulate oxide composition.
  • the silver zinc zeolite can be mixed with the particulate oxide composition to yield a blended composition.
  • the blended composition is about 10% wt/wt silver zinc zeolite and about 90% wt/wt particulate oxide composition.
  • the physical mixing can occur by placing the silver zinc zeolite and the particulate oxide composition in a sealed container and then the container is shaken, inverted repeatedly, tumbled, or similar action.
  • the physical mixing can occur by placing silver zinc zeolite and the particulate oxide composition in a device designed to mix dry powder materials, such as a blender, paddle mixer, or the like. In any mixing method, the mixing should occur for an amount of time that achieves a homogeneous mixture of the materials.
  • the supported composition independently may be used for treating gaseous or aqueous mixtures. Or the supported composition may be incorporated into an article specifically designed for treating gaseous or aqueous mixtures, such as a filter or a plastic container.
  • the filter may be a fixed bed. The filter may be used for a gaseous or aqueous mixture or stream and thus to filter the gaseous or aqueous mixture or stream.
  • the blended composition is deposited onto a support material or within the support material to provide the supported composition for removing biological contaminants.
  • the blended composition can be deposited on one or more external and/or internal surfaces of the support material. It can be appreciated that persons of ordinary skill in the art generally refer to the internal surfaces of the support material as pores.
  • the blended composition as described herein can be supported on the support material with or without a binder. In some embodiments, the blended composition can be applied to the support material using any conventional techniques, such as slurry deposition.
  • Processes of preparing the supported compositions are not limited by any particular steps or methods, and generally can be any that result in the incorporation of the blended composition into a support material or deposited onto a support material.
  • Processes to incorporate the blended composition into a support material include mixing the blended composition into the support material production.
  • the blended composition can be added to molten polypropylene in the molding process.
  • the blended composition can be added to a mixture of polyvinyl chloride resin, a plasticizer, and a stabilizer and passed through a hot mixer followed by an extruder.
  • the organic binder is selected from the group consisting of citric acid, polyurethane diol, polyvinyl alcohol, polyvinylpyrollidone, linseed oil, and mixtures thereof.
  • the support as coated optionally may be rinsed with water prior to drying to remove residual not bound to the support.
  • the coated support can then be optionally dried at temperatures above about 20°C and below about 300°C for about 1-12 hours or until sufficiently dry. In certain embodiments, the coated support can then be optionally dried at temperatures above about 20°C and below about 120°C.
  • the support can be heated to the point where the surface just begins to soften, then the blended composition can be placed on the surface such that it begins to mix with the semi-molten material. Upon cooling and resolidifying the blended composition is incorporated into the surface of the support material.
  • the temperature utilized would depend on the support material utilized. One of skill in the art readily would be able to determine the appropriate temperature for the support material being utilized. For example, this temperature for quartz glass would be over 1000°C; borosilicate glass would be about 500-600°C; and PVC would be about 200-300°C.
  • These solid supports can be utilized to form articles including filters and plastic articles.
  • the blended compositions also may be incorporated into an article for a high touch surface and this high touch surface may come into contact with biological contaminants by direct touch contact.
  • articles for high touch surfaces also may be utilized in reducing bacteria and/or viruses deposited through contact and not necessarily just in treating fluids. These articles may be containers for liquids, elevator buttons, hand railing covers for escalators or stairs, a door, door handle, doorknob, coverings on public transportation, touch pads for electronic transactions, fabrics, and the like.
  • supported compositions comprising the blended composition and support material may be used independently in methods for removing biological contaminants, or the supported compositions of the blended composition and support material may be incorporated into an article specifically designed for treating gaseous or aqueous mixtures, such as a filter or a plastic (such as a plastic container).
  • the particulate oxide compositions comprise cerium oxide; trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof; and optionally an additional metal oxide selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof, wherein the cerium oxide is present in an amount greater than the trivalent dopant and wherein the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate oxide composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate composition.
  • trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof
  • an additional metal oxide selected from
  • the present application relates to methods for removing and ensuring a target concentration or less of biological contaminants using the disclosed blended compositions containing silver zinc zeolite and trivalent doped cerium oxide.
  • biological contaminants include bacteria, viruses, protozoa (e.g., amoebae), fungi, algae, yeast, and the like.
  • These methods can use the blended compositions per se, supported compositions containing the blended compositions, and articles containing supported compositions containing the blended compositions.
  • an aqueous or gaseous stream is contacted with the blended composition of silver zinc zeolite and the particulate oxide compositions.
  • the particulate oxide compositions include all of the embodiments described supra, including any of the above-described amounts of trivalent dopant, cerium oxide, and optional additional metal oxide, and any of the above-described properties.
  • an aqueous or gaseous stream is contacted with the supported compositions containing the blended compositions as described herein.
  • a potentially contaminated surface is contacted with the supported compositions or articles containing the blended compositions as described herein.
  • These potentially contaminated surfaces include, for example, skin (e.g., a hand, finger, palm, etc.) and the contact is through touching the supported compositions or articles containing the blended compositions as described herein.
  • the biological contaminant to be removed may be contained within an aqueous or gaseous stream or may be on the surface of the physical object.
  • the contacting of the blended composition containing silver zinc zeolite and particulate oxide composition as described herein with the biological contaminant leads to the biological contaminant one or more of sorbing and/or reacting with the silver zinc zeolite and/or trivalent doped cerium oxide or deactivating when contacted with the silver zinc zeolite and/or trivalent doped cerium oxide.
  • the sorbing, reacting, and/or deactivating of the biological contaminant with the silver zinc zeolite and/or trivalent doped cerium oxide removes the biological contaminant from the biological contaminant-containing fluid (air or aqueous stream) or the solid surface.
  • the unique depth profile for the particulate oxide compositions such that there is a higher ratio of trivalent dopant to cerium on and closer to the surface may provide improved activity for removing biological contaminants. It is surprising that the blended compositions exhibit improved activity in comparison to the silver zinc zeolite or the particulate oxide compositions alone.
  • the biological contaminant may be removed to a target level or to below a target level.
  • the biological contaminant may be removed to a level at which it is undetectable.
  • the target level may be a specified amount or the limit of detection.
  • the biological contaminant to be removed may be identified and the target amount or level for the contaminant may be set. For certain of the biological contaminants contemplated herein, the target amount or level would be any detectable amount.
  • the methods optionally may additionally comprise monitoring the treated stream for the contaminant.
  • the methods disclosed herein may be used to treat air or water or may be used to treat contaminants through contact by touch.
  • the disclosed blended compositions are incorporated into a high touch surface.
  • the blended compositions may be incorporated into a supported composition and those supported composition may be incorporated into an article specifically designed for treating gaseous or aqueous mixtures, such as a filter, a fixed bed filtration system, or in a plastic for a container.
  • the blended compositions also may be used per se and contacted through slurrying. In these methods involving slurrying, the method may further comprise filtering the fluid/liquid.
  • the particulate oxide compositions within the blended compositions can have any of the above-described amounts of trivalent dopant, cerium oxide, and optional additional metal oxide, and any of the above-described properties.
  • the particulate oxides compositions within the blended composition have the unique depth profile.
  • the blended compositions can have any of the abovedescribed amounts of silver zine zeolite and particulate oxide compositions.
  • the methods of the disclosure are envisioned for removing biological (e.g., bacterial, viral, amoebae, etc.) contaminants from air and/or drinking water and groundwater, it will be understood that the process can be used to treat any gaseous or aqueous liquid feed that contains undesirable amounts of biological contaminants.
  • the methods also are envisioned for removing biological contaminants through direct contact of a contaminated surface with an article containing the blended compositions as disclosed herein.
  • these methods of removing biological contaminants comprise (i) providing a blended composition comprising (a) silver zinc zeolite and (b) particulate oxide composition comprising cerium oxide; trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof; and optionally an additional metal oxide selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof, wherein the cerium oxide is present in an amount greater than the trivalent dopant and wherein the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate composition; (ii) contacting the blended composition with a biological contaminant wherein the biological contaminant is
  • the blended composition may be contained within a supported composition and in certain of these embodiments, the supported composition may be incorporated into an article.
  • These methods may further comprise monitoring for the biological contaminant after contacting. The monitoring may be done by sampling or may be continuous.
  • these methods comprise (i) providing a supported composition comprising a support material comprising an organic polymer, cotton, glass fiber, or mixtures thereof and a blended composition, wherein the blended composition comprises (a) silver zinc zeolite and (b) particulate oxide composition comprising cerium oxide, trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof, and optionally an additional metal oxide selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof, wherein the cerium oxide is present in an amount greater than the trivalent dopant and wherein the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate composition
  • the particulate oxide composition within the blended composition comprises cerium oxide in an amount of about 99.9 wt % to about 20 wt % based on the total weight of the particulate oxide composition; trivalent dopant in an amount of about 0.1 wt % up to about 50 wt % based on the total weight of the particulate oxide composition; and additional metal oxide in an amount of about 70 wt % to about 0 wt % based on the total weight of the particulate oxide composition.
  • the biological contaminant can be contained in an aqueous or liquid stream or on the surface of an object that is physically contacted with the supported composition. These methods may further comprise monitoring for the biological contaminant after contacting. The monitoring may be done by sampling or may be continuous.
  • the blended compositions include any of the above-described amounts of silver zinc zeolite and particulate oxide composition, and the particulate oxide compositions as used include all of the embodiments as described supra, including any of the above-described amounts of trivalent dopant, cerium oxide, and optional additional metal oxide, and any of the above-described properties.
  • the particulate compositions having the unique depth profile are particularly capable of reducing the concentration of biological contaminants in combination with the silver zinc zeolites.
  • the contacting of the blended composition with the biological contaminant leads to removal of a measurable amount of the biological contaminant. In some embodiments, the contacting removes at least about 90% of the biological contaminant. In other embodiments, the contacting removes at least 95%, or more preferably 99% or 99%+ of the biological contaminant.
  • the contacting of the blended composition with the biological contaminant can reduce its concentration by more than about 75%. More typically, the contacting of the blended composition with the biological contaminant can reduce its concentration by more than about 80%, more typically more than about 85%, more typically more than about 90%, more typically more than about 95%, more typically more than about 97.5%, more typically more than about 99%, and even more typically more than about 99.5%.
  • these methods may be for removing biological contaminants from fluid or for treating fluid.
  • the fluid may be a gaseous, aqueous stream, or mixture thereof.
  • the methods may use either the blended compositions per se, a supported composition, or an article as described herein.
  • the methods comprise (i) providing a blended composition, supported composition, or article as described herein. If in a supported composition, the support material comprises an organic polymer, cotton, glass fiber, or mixtures thereof.
  • the blended composition comprises (a) silver zinc zeolite and (b) particulate oxide composition comprising: cerium oxide; trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof; and optionally an additional metal oxide selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof, wherein the cerium oxide is present in an amount greater than the trivalent dopant and wherein the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate composition.
  • cerium oxide selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (P
  • the method further comprises (ii) contacting a biological contaminant containing gaseous or aqueous stream with the blended composition, wherein the biological contaminant is selected from the group consisting of bacteria, viruses, fungi (e.g., mold), protozoa (e.g., amoebae), and mixtures thereof; and (iii) removing biological contaminant from the gaseous or aqueous stream through contact with the blended composition.
  • the biological contaminant can be removed in an amount of 90% or more.
  • These methods may further comprise monitoring for the biological contaminant after contacting. The monitoring may be done by sampling or may be continuous.
  • the blended composition and the particulate oxide compositions within the blended composition include all of the embodiments as described supra.
  • the particulate oxide compositions in combination with the silver zinc zeolites are capable of reducing the concentration of biological contaminants.
  • the method may further comprise a step of setting a target concentration of biological contaminant.
  • a biological contaminant of interest is identified and then a target concentration for that biological contaminant is set.
  • the methods additionally may comprise a step of monitoring the biological contaminant in the treated stream. The monitoring may be done by sampling or may be continuous.
  • the methods comprise the steps of (i) providing a composition comprising a support material comprising an organic polymer, cotton, glass fiber, or mixtures thereof and particulate oxide composition comprising cerium oxide; trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof; and optionally an additional metal oxide selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof, wherein the cerium oxide is present in an amount greater than the trivalent dopant and wherein the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the particulate composition; (ii) setting a target concentration of a biological contaminant; (i)
  • the particulate oxide compositions as used in these methods include all of the embodiments as described supra.
  • the target concentration can be set at a certain amount of contaminant (e.g., virus, bacteria, protozoa/amoebae, or fungi) or can be set at the limit of detection.
  • Monitoring of the biological contaminant can be performed through techniques well known to those of skill in the art. The monitoring may be done by sampling or may be continuous.
  • One of skill in the art understands real-time and continuous monitoring techniques for microbial contaminants, including viruses, bacteria, protozoa/amoebae, fungi, and the like. These techniques include optical techniques and cell counters.
  • These methods may further comprise monitoring for the biological contaminant after contacting.
  • the monitoring may be done by sampling or may be continuous.
  • the methods may further comprise setting a target concentration of a biological contaminant and monitoring the treated aqueous stream for the biological contaminant.
  • the target concentration may be a specified amount or the limit of detection.
  • the blended composition may be contained within a supported composition or within a supported composition within an article or may be contacted by slurrying the blended composition per se with the aqueous stream.
  • the method may further comprise filtering the fluid/liquid.
  • the blended composition and the particulate oxide composition within the blended composition as used in these methods include all of the embodiments as described supra.
  • the methods comprise (i) providing a supported composition comprising a support material comprising an organic polymer, cotton, glass fiber, or mixtures thereof and a blended composition comprising (a) silver zinc zeolite and (b) particulate composition comprising cerium oxide; trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof; and optionally an additional metal oxide selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof, wherein the cerium oxide is present in an amount greater than the trivalent dopant and wherein the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the surface of the
  • the blended compositions and particulate oxide compositions as used in these methods include all of the embodiments as described supra. These methods may further comprise monitoring for the biological contaminant after contacting. The monitoring may be done by sampling or may be continuous. In specific embodiments the methods may further comprise setting a target concentration of a biological contaminant and monitoring the treated aqueous stream for the biological contaminant.
  • the target concentration may be a specified amount or the limit of detection.
  • the methods comprise the methods comprise (i) providing a supported composition comprising a support material comprising an organic polymer, cotton, glass fiber, or mixtures thereof and a blended composition comprising (a) silver zinc zeolite and (b) particulate composition comprising cerium oxide; trivalent dopant selected from the group consisting of yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), and mixtures thereof; and optionally an additional metal oxide selected from the group consisting of aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and mixtures thereof, wherein the cerium oxide is present in an amount greater than the trivalent dopant and wherein the average trivalent dopant to Ce ratio at about 0 nm to about 3.5 nm from the surface of the particulate composition is greater than the trivalent dopant to Ce ratio at about 15 nm from the
  • the blended compositions and particulate oxide compositions as used in these methods include all of the embodiments as described supra. These methods may further comprise monitoring for the biological contaminant after contacting. The monitoring may be done by sampling or may be continuous. In specific embodiments the methods may further comprise setting a target concentration of a biological contaminant and monitoring the treated gaseous stream for the biological contaminant. The target concentration may be a specified amount or the limit of detection.
  • the removal can be expressed as a % reduction that is determined by using Colony Forming Units (CFU).
  • CFU Colony Forming Units
  • the concentration of bacteria contaminant after contacting with the blended composition or a supported composition or article comprising the blended composition can be about 45 colony forming units CFU/ml to 5xl0 5 CFU/ml.
  • the removal can be expressed as a % reduction that is determined by using Most Probable Number (MPN) technique.
  • MPN Most Probable Number
  • MPN is used to estimate the concentration of viable microorganisms in a sample by means of replicating liquid broth growth in ten-fold dilutions.
  • a target concentration for biological contaminant also can be set as a percentage reduction of the contaminant from prior to the method and then after contact in the method. In certain embodiments, this percent reduction can be about 75% to about 100% less. In other embodiments, this percent reduction can be about 80% to about 99.9%.
  • a target concentration for biological contaminant can be set at a limit of detection for that contaminant.
  • the methods may further comprise one or more of the following additional steps: identifying the biological contaminant of interest; setting the target concentration; and monitoring for the biological contaminant after the contacting step to determine or verify that the biological contaminant is below the target concentration.
  • the target concentration can be any detectable amount of that contaminant and the methods as disclosed herein are effective in treating the aqueous or gaseous stream as long as no amount of that contaminant is detected in the treated stream.
  • the stream to be treated is a gaseous stream and the targeted contaminant is paramyxovirus, Mycobacterium tuberculosis, coronavirus, or a mixture thereof.
  • the viruses to be targeted are transmitted primarily by touch and include varicella-zoster virus (VZV), variola virus (including smallpox and monkey pox).
  • the target concentration can be set at a certain amount of contaminant or can be set at the limit of detection.
  • the method also can include a step of identifying the contaminant of interest prior to setting the target concentration.
  • the blended compositions and particulate oxide compositions as used in this method include all of the embodiments as described supra.
  • the blended composition of step (i) also can be provided as part of a supported composition, and as such, further comprise a support material comprising an organic polymer, cotton, glass fiber, or mixtures thereof or as part of an article comprising a supported composition.
  • Examples of gaseous feeds that can be treated according to the methods as disclosed herein include, among others, building ventilation systems, aircraft or vehicle ventilation systems, and ambient room air.
  • Examples of liquid feeds that can be treated according to the methods as disclosed herein include, among others, tap water, well water, surface waters, such as water from lakes, ponds and wetlands, waters for recreational activities, agricultural waters, wastewater from industrial processes, and geothermal fluids.
  • Examples of other uses involving physical contact with biological contaminants rather than filter include incorporation into a plastic for a container or a plastic to be incorporated into a high touch surface, such as elevator buttons, escalator railing covers, stair railing covers, touch pads for electronic transactions, doors, doorknobs, and the like. These high touch surfaces also may include glass or a mixture of glass and plastic.
  • the process is envisioned for removing biological contaminants from a gaseous or an aqueous stream using the blended compositions comprising silver zinc zeolite and particulate oxide compositions.
  • the gaseous stream can be one or more of an ambient air source or more supply air for a ventilation system that contains or may contain undesirable amounts of biological and/or other contaminants.
  • the aqueous stream can be one or more of a drinking water and groundwater source that contains or may contain undesirable amounts of biological and/or other contaminants.
  • the aqueous stream can include without limitation well waters, surface waters (such as water from lakes, ponds, and wetlands, including natural and man-made and water for recreational purposes), agricultural waters, wastewater from industrial processes, and geothermal waters.
  • the biological contaminant-containing gaseous stream is passed through an inlet into a vessel at a temperature and pressure, usually at ambient temperature and pressure, such that the gas in the biological contaminant-containing gaseous stream remains in the gaseous state.
  • the biological contaminantcontaining gaseous stream is contacted with the blended composition.
  • the contacting of the blended composition with the biological contaminant-containing gaseous stream removes the biological contaminant.
  • the contacting of the blended composition with the biological contaminant-containing gaseous stream leads to removal of a measurable amount of the biological contaminant and in some embodiments removal of at least 90%, more preferably 95%, and even more preferably 99% or 99%+ of the biological contaminant.
  • the blended compositions and particulate oxide compositions as used in these methods including all of the embodiments as described supra.
  • the blended composition is in the form of a fixed bed.
  • the fixed bed containing the blended composition normally comprises particles containing the trivalent doped cerium oxide and particles of silver zinc zeolite.
  • the blended composition can have a shape and/or form that exposes a maximum trivalent doped cerium oxide particle surface area to the gaseous or aqueous fluid with minimal back-pressure and the flow of the gaseous or aqueous fluid through the fixed bed.
  • the blended composition may be in the form of a shaped body such as beads, extrudates, porous polymeric structures or monoliths.
  • the blended composition can be supported as a layer and/or coating on such beads, extrudates, porous polymeric structures or monolith supports.
  • the blended compositions can be used to treat any biological contaminant, and in particular bacteria, viruses, protozoa (e.g., amoebae), fungi, yeast, and mixtures thereof.
  • the contacting of the blended composition with the biological contaminant can reduce its concentration by more than about 75%. More typically, the contacting of the blended composition with the biological contaminant can reduce its concentration by more than about 80%, more typically more than about 85%, more typically more than about 90%, more typically more than about 95%, more typically more than about 97.5%, more typically more than about 99%, and even more typically more than about 99.5%.
  • the biological contaminant is bacteria or mold
  • the % reduction can be determined by number using Colony Forming Units (CFU).
  • CFU Colony Forming Units
  • MPN Most Probable Number
  • the method of treating air or water to remove biological contaminants comprises the steps of passing an air or water stream containing a first concentration of one or more undesired biological contaminants through a material, article, or supported composition comprising the blended composition and obtaining a treated air or water stream having a concentration of one or more undesired biological contaminants less than the first concentration.
  • the biological contaminants to be removed are viruses.
  • the concentration of virus can be equal to or less than a target concentration of virus.
  • the contacted (or treated) stream has a concentration of virus equal to or less than a target concentration of virus.
  • the viruses are coronavirus.
  • the biological contaminants to be removed are bacteria.
  • the concentration of bacteria can be equal to or less than a target concentration of bacteria.
  • the contacted (or treated) stream has a concentration of bacteria equal to or less than a target concentration of bacteria.
  • the bacteria are fecal coliform bacteria.
  • the biological contaminants to be removed are protozoa (e.g., amoebae).
  • the concentration of protozoa e.g., amoebae
  • the concentration of protozoa can be equal to or less than a target concentration of protozoa (e.g., amoebae).
  • the contacted (or treated) stream has the concentration of protozoa (e.g. amoebae) equal to or less than a target concentration of protozoa (e.g., amoebae).
  • the protozoa (e.g., amoebae) to be removed are Naegleria fowleri and/or Cryptosporidum.
  • the biological contaminants to be removed are fungi (e.g., mold).
  • the concentration of fungi can be equal to or less than a target concentration of fungi.
  • the contacted (or treated) stream has a concentration of fungi equal to or less than a target concentration of fungi.
  • the fungi to be removed are Trichophyton mentagrophytes and/or Aspergillus.
  • the concentration of contaminant after contacting with a supported composition or material or article comprising the blended composition can be about 45 colony forming units CFU/ml to 5xl0 5 CFU/ml.
  • the target concentration can be set at a certain amount of contaminant (e.g., virus, bacteria, amoeba, fungi) CFU per ml or can be set at the limit of detection.
  • the blended composition per se is slurried with the biological contaminant-containing aqueous stream. It can be appreciated that the blended composition of silver zinc zeolite and particulate oxide composition and the biological contaminant-containing aqueous stream are contacted when they are slurried. While not wanting to be bound by any theory, it is believed that some, if not most or all of the biological contaminant contained in the biological contaminant-containing aqueous stream is removed from the biological contaminant-containing aqueous stream by the slurring and/or contacting of the blended composition comprising trivalent doped cerium oxide particulate composition and silver zinc zeolite with the biological contaminant-containing aqueous stream.
  • the slurry is filtered by any known solid liquid separation method.
  • the blended composition and particulate oxide composition utilized in methods including slurrying include all of the embodiments as described herein.
  • the peak width at half height was used to determine the crystallite size.
  • the zeta potential vs. pH was measured using a Malvern Panalytical (Zetaziser Nano ZS) ZEN3600 using a procedure similar to ASTM E2865-12(2018).
  • crystallite sizes are measured by XRD or TEM and are the size of the individual crystals.
  • the D xx sizes are the size of the particles that are made-up of the individual crystallites and is measured by laser diffraction.
  • the temperature programmed desorption of CO2 was performed as described in Hakim, A. et al. Temperature Programmed Desorption of Carbon Dioxide for Activated Carbon supported Nickel Oxide: The Adsorption and Desorption Studies, Advanced Materials Research, Vol.
  • a trivalent doped cerium oxide composition was prepared by the following method. 68 g (0.297 mol) of lanthanum carbonate and 464 g (2.7 mol) cerium oxide were mixed with 200 ml of a 1.0 mol/L lanthanum nitrate solution. The ingredients were mixed for 2 hours. The mixture was then heated in a furnace to 550°C for 2 hours to obtain 542 g of a mixed cerium lanthanum oxide which is approximately 15% lanthanum oxide by weight. This could also be called a La doped cerium oxide.
  • SEM Scanning electron microscope
  • TEM Transmission electron microscope
  • a sample of the example 1 composition was analyzed for surface area, pore radius, and pore volume and found to be 98.332 m 2 /g (BET) and 135.268 m 2 /g (BJH) with a pore radius of 3.235 nm and pore volume of 0.248 cc/g.
  • the measured Hg-porosity was measured to be 0.21 cc/g, with pore size ⁇ 1 pm was 0.46 cc/g, and the total pore volume was 0.96 cc/g.
  • the particle size distribution was measured as described above with the results being D10 3.552 pm, D50 12.1 pm, and D90 43.12 pm.
  • the crystallite size as measured by XRD was determined to be 9.77 nm.
  • the temperature programmed desorption profile is Fig 5A. The desorption of CO2 had 3 peak temperatures 172°C, 350°C and 735°C indicating both physisorption and chemisorption of CO2.
  • the H2 TPR is depicted in Fig 6 and shows an intense peak around 500°C in stark contrast to examples 2 and 3 which had broader peaks.
  • the zeta-potential as a function of pH is presented in Fig. 7.
  • the isoelectric point (IEP) was found to be 8.1.
  • the ratio of LaO + to 140 CeO + as a function of depth is plotted in Fig. 8. It should be noted the LaO + to CeO + ratio is higher at shallower depths and approaches a constant level as the depth increases. This indicates the concentration of La is higher on the surface and closer to the surface for the material from Example 1.
  • the Example 1 material is an embodiment of the trivalent doped cerium oxide having the unique depth profile.
  • a trivalent doped cerium oxide composition was prepared by the following method also as described in U.S. Patent Application No. 17/870,068. 129 ml of a 1 mol/L Ce(NO3)4 solution was mixed with 24 ml of a 1 mol/L La(NOs)3 solution. The resulting solution was heated to reflux for at least 2 hours. 5.5 mol/L NH4OH was then added to a pH of 10. The resulting solid was filtered and washed with DI water until the wash water was ⁇ 15 mS/cm. The resulting powder was heated in a furnace in air at 550°C for at least 2 hours to obtain a mixed cerium lanthanum oxide which is approximately 15% lanthanum oxide by weight. This could also be called a La doped cerium oxide.
  • Figures 10 and 11 are the SEM images. The images reveal a porous material that somewhat spherical in shape.
  • Figures 12A-12D contains the TEM images. The images reveal clusters of spheres and diffraction planes can be seen. The surface area was found to be 120.464 m 2 /g (BET) and 143.087 m 2 /g (BJH) with a pore radius of 3.245 nm and pore volume of 0.285 cc/g. The measured pore volume with pore size ⁇ 0.1 pm was measured to be 0.23 cc/g, with pore size ⁇ 1 pm was 0.45 cc/g, and the total pore volume was 0.99 cc/g.
  • the particle size distribution was measured as described above with the results being D10 1.301 pm, D50 5.545 pm, and D90 13.109 pm.
  • the crystallite size as measured by XRD was determined to be 9.03 nm.
  • the temperature programmed desorption profile is Fig 5B.
  • the desorption of CO2 had 1 peak temperature at 175°C indicating only physisorption of CO2. Any peaks at higher temperatures are not distinguished from the background and thus chemisorption of CO2 is not detected.
  • the H2 TPR is depicted in Fig 6 and shows a broad peak around 566°C.
  • the zeta-potential as a function of pH is presented in Fig. 7.
  • the isoelectric point (IEP) was found to be 7.34.
  • a cerium (IV) oxide composition was prepared by the following method.
  • a one liter of a 0.12 M cerium (IV) ammonium nitrate solution was prepared from cerium (IV) ammonium nitrate crystals dissolved in nitric acid and held at approximately 90°C for about 24 hours.
  • a separate container 200 ml of a 3M ammonium hydroxide solution was prepared and held at room temperature. Subsequently the two solutions were combined and stirred for approximately one hour. The resultant precipitate was filtered using Buchner funnel equipped with filter paper. The solids were then thoroughly washed in the Buchner using deionized water.
  • the wet hydrate was calcined in a muffle furnace at approximately 450°C. for three hours to form the cerium (IV) oxide composition.
  • the surface area was found to be 126 m 2 /g (BET) and 167 m 2 /g (BJH) with a pore radius of 3.62 nm and pore volume of 0.309 cc/g.
  • the measured pore volume with pore size ⁇ 0.1 pm was measured to be 0.24 cc/g, with pore size ⁇ 1 pm was 0.35 cc/g, and the total pore volume was 0.85 cc/g.
  • the particle size distribution was measured as described above with the results being D10 2 pm, D50 9 pm, and D90 25 pm.
  • the crystallite size as measured by XRD was determined to be 8.43 nm.
  • the temperature programmed desorption profile is Fig 5C.
  • the desorption of CO2 had 1 peak temperature at 175°C indicating only physisorption of CO2. Any peaks at higher temperatures are not distinguished from the background and thus chemisorption of CO2 is not detected.
  • the H2 TPR is depicted in Fig 6 and shows broad peaks around 500 and 900°C.
  • the zeta-potential as a function of pH is presented in Fig. 7.
  • the isoelectric point (IEP) was found to be 7.22.
  • a trivalent doped cerium oxide composition was prepared by the following method.
  • a one liter of a 0.12 M cerium (IV) ammonium nitrate solution was prepared from cerium (IV) ammonium nitrate crystals dissolved in nitric acid.
  • 199.5 g (0.5 mol) commercially available Al(NOs)3 was added to a separate container 200 ml of a 3M ammonium hydroxide solution was prepared and held at room temperature.
  • the two solutions were combined and stirred for approximately one hour.
  • the resultant precipitate was filtered using Buchner funnel equipped with filter paper.
  • the solids were then thoroughly washed in the Buchner using deionized water.
  • the wet hydrate was calcined in a muffle furnace at approximately 450°C for three hours to form an aluminum cerium (IV) oxide composition.
  • This oxide was suspended in a Praseodymium nitrate solution containing Praseodymium carbonate.
  • the Pr to aluminum cerium (IV) oxide ratio was varied to achieve a 4%, 8%, 12% or 20% loading of Pr oxide on the final product.
  • the ingredients were mixed for 2 hours.
  • the mixture was then heated in a furnace to 550°C for 2 hours to obtain a mixed cerium aluminum praseodymium oxide. This could also be called a Pr doped cerium oxide.
  • Example 4 The depth profile of each of these materials was then measured and the PrO + to 140 CeO + ratio vs depth is presented in Fig. 9. As with Example 1 the trivalent, in this case PrO + , to 140 CeO + ratio is higher at the surface and shallower depths and approaches a constant level as the depth increases.
  • the Example 4 materials are embodiments of the trivalent doped cerium oxide having the unique depth profile.
  • a praseodymium doped cerium oxide composition was prepared by the following method. This method is similar to the method of Example 2. 129 ml of a 1 mol/L Ce(NO3)4 solution was mixed with 82 ml of a 1 mol/L Pr(NOs)3 solution and 63.9 g (0.3 mol) commercially available A1(NO3)3. The resulting solution was heated to reflux for at least 2 hours. 5.5 mol/L NH4OH was then added to a pH of 10. The resulting solid was filtered and washed with DI water until the wash water was ⁇ 15 mS/cm. The resulting powder was heated in a furnace in air at 550°C for at least 2 hours to obtain a mixed cerium aluminum praseodymium oxide which contains approximately 16% Pr oxide by weight. This could also be called a Pr doped cerium oxide.
  • a commercially available inorganic antimicrobial agent was obtained from a supplier (Surfatas) under the commercial name Life DJ7 AM-00-1 A (CAS# 130328-20- 0).
  • the product literature describes this material as having a silver content of 2.5% and a zinc content of 10-16%. The remainder of this material is a zeolite. It is registered as a pesticide with the EPA under EPA Registration No. 71227-1-85576.
  • this material can be made by the method described in lyigiindogdu et al. Development of durable antimicrobial surfaces containing silver- and zinc-ion-exchanged zeolites, Turkish Journal of Biology, Vol. 38: No. 3, Article 14, (2014) pp 420-427.
  • this method involves the hydrothermal synthesis of the zeolite followed by ion-exchange of the sodium (Na) contained in the zeolite with silver (Ag) and zinc (Zn) by treatment with individual solutions of AgNCh and ZnCh.
  • Example 1 a measured amount of the composition of example 1 was placed in a container along with a measured amount of the material from example 6.
  • 9 g of example 1 was placed in a 60 ml polyethylene bottle.
  • 1 g of example 6 was added.
  • the bottle was sealed and placed in a tumbler which rotated the bottle in such a way that the bottle was inverted once per second.
  • the bottle was tumbled in this fashion for at least 1 hr.
  • No chemical reaction was expected.
  • the materials were only blended together as dry powders.
  • the blended powders were characterized by measuring the BET surface area and pore radius. BHJ methods are not valid for zeolites which makes the pore volume meaningless, thus the BHJ surface area and pore volume are not reported. The results are compiled in Table 2.
  • Example 7B The material of Example 7B was prepared and characterized as in example 7 A with the exception of 7.5 g of example 1 was used and 2.5 g of example 6 was used to yield a mixture that is 75% example 1 and 25% example 6.
  • Example 7C The material of Example 7C was prepared and characterized as in example 7A with the exception of 5.0 g of example 1 was used and 5.0 g of example 6 was used to yield a mixture that is 50% example 1 and 50% example 6.
  • the particle size distribution D50, D90, and DI 00 were also measured for this blend and the results are compiled in Table 2.
  • Example 7D The material of Example 7D was prepared and characterized as in example 7A with the exception of 2.5 g of example 1 was used and 7.5 g of example 6 was used to yield a mixture that is 25% example 1 and 75% example 6.
  • Example 3 a measured amount of the composition of example 3 was placed in a container along with a measured amount of the material from example 6.
  • 9 g of example 3 was placed in a 60 ml polyethylene bottle.
  • 1 g of example 6 was added.
  • the bottle was sealed and placed in a tumbler which rotated the bottle in such a way that the bottle was inverted once per second.
  • the bottle was tumbled in this fashion for at least 1 hr.
  • No chemical reaction was expected.
  • the materials were only blended together as dry powders.
  • the blended powders were characterized by measuring the BET surface area, pore radius, pore volume. The results are compiled in Table 2.
  • Example 8B The material of Example 8B was prepared and characterized as in example 8 A with the exception of 7.5 g of example 3 was used and 2.5 g of example 6 was used to yield a mixture that is 75% example 3 and 25% example 6.
  • Example 8C The material of Example 8C was prepared and characterized as in example 8 A with the exception of 5.0 g of example 3 was used and 5.0 g of example 6 was used to yield a mixture that is 50% example 3 and 50% example 6.
  • Example 8D The material of Example 8D was prepared and characterized as in example 8A with the exception of 2.5 g of example 3 was used and 7.5 g of example 6 was used to yield a mixture that is 25% example 3 and 75% example 6.
  • Example 1 Bacterial Removal Characteristics of the composition of Example 1, 3, 6, 7A- D, and 8B-C were tested using an adapted EN 13727 method. Suspensions of these materials (0.2 g/ml in deionized water) in the amount of 4 ml were added to a mixture of 0.5 ml Methicillin resistant Staphylococcus aureus (MRSA) ATCC® 43300TM suspension and 0.5 ml hard water at room temperature (20 ⁇ 1°C). At 1 hour, 0.5 mL of mixture was transferred to a tube containing 4 mL neutralizer (Dey Engley broth) and incubated for 5 min ⁇ 10 s at 20°C ⁇ 1°C.
  • MRSA Methicillin resistant Staphylococcus aureus
  • example 7A The material of example 7A is suspended in deionized water and a binder, such as citric acid, is added to the water.
  • a substrate such as cotton fabric
  • a substrate such as cotton fabric
  • a substrate is then immersed in the suspension at least one time. After removing the substrate, it is allowed to dry.
  • the resulting fabric has a coating of the composition of example 7A its surface.
  • This coated fabric is then placed in a funnel such that fabric will remain in the funnel when water is passed through. Water contaminated with E. coli is then poured into the funnel and comes in contact with the coated fabric.
  • the water collected from the funnel is analyzed and found to have a reduced concentration of E. coli.
  • the material of example 7A is suspended in deionized water and a binder, such as citric acid, is added to the water.
  • a substrate such as cotton fabric
  • a substrate such as cotton fabric
  • a substrate is then immersed in the suspension at least one time. After removing the substrate, it is allowed to dry.
  • the resulting fabric has a coating of the composition of example 1 its surface.
  • This coated fabric is then placed on an air filter such that fabric covers the face of the air filter and air can pass though the fabric.
  • the filter is then placed in an HVAC or room air filtration unit. Upon turning on the unit, air contaminated with coronavirus is passed through the filter. The air discharged from the unit is analyzed and found to have a reduced concentration of coronavirus.
  • Polyethylene granules or powder is mechanically mixed with the material of example 7A such that the material of example 7A is approximately 1% by weight.
  • the mixture is then fed into a heating chamber to form an end use product such as a bottle.
  • the surface to the polyethylene is tested for antibacterial or bacteriostatic properties by exposing the surface to E. coli.
  • the surface is then analyzed for E. coli and found to have less colony forming units than a control.
  • Another test is conducted by putting pasteurized milk in the formed bottle and observing the time necessary for the milk to spoil. Compared a polyethylene bottle without the material of example 7 A, the milk takes a longer time to spoil.
  • compositions and methods described herein are well adapted to attain the ends and advantages mentioned as well as those inherent therein.
  • Those skilled in the art will recognize that the methods and systems within this specification may be implemented in many manners and as such are not to be limited by the foregoing exemplified embodiments and examples. In this regard, any number of the features of the different embodiments described herein may be combined into one single embodiment and alternate embodiments having fewer than or more than all of the features herein described are possible.

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EP24706285.4A 2023-01-11 2024-01-11 Gemischte zusammensetzungen zur entfernung biologischer verunreinigungen mit dreiwertigem dotiertem ceroxid und silberzinkzeolith Pending EP4648613A1 (de)

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